Is it possible to remove polymeric nanoparticles from aqueous paints during the activated sludge treatment?

The market for emulsion polymers (latexes) is large and growing at the expense of other manufacturing processes that emit higher amounts of volatile organic solvents. The paint industry is not an exception and solvent-borne paints have been gradually substituted by aqueous paints. In their life-cycle, much of the aqueous paint used for architectural or decorative purposes will eventually be discharged into wastewater treatment facilities, where its polymeric nanoparticles (mainly acrylic and styrene-acrylic) can work as xenobiotics to the microbial communities present in activated sludge. It is well established that these materials are biocompatible at macroscopic scale. But is their behaviour the same at nanoscale? What happens to the polymeric nanoparticles during the activated sludge process? Do nanoparticles agregate and are discharged together with the sludge or remain in emulsion? How do microorganisms interact with these nanoparticles? Are nanoparticles degradated by them? Are they adsorbed? Are these nanoparticles toxic to the microbial community? To study the influence of these xenobiotics in the activated sludge process, an emulsion of cross-linked poly(butyl methacrylate) nanoparticles of ca. 50 nm diameter was produced and used as model compound. Activated sludge from a wastewater treatment plant was tested by the OCDE’s respiration inhibition test using several concentrations of PBMA nanoparticles. Particle aggregation was followed by Dynamic Light Scattering and microorganism surfaces were observed by Atomic Force Microscopy. Using sequential batch reactors (SBRs) and continuous reactors, both inoculated with activated sludge, the consumption of carbon, ammonia, nitrite and nitrate was monitored and compared, in the presence and absence of nanoparticles. No particles were detected in all treated waters by Dynamic Light Scattering. This can either mean that microorganisms can efficiently remove all polymer nanoparticles or that nanoparticles tend to aggregate and be naturally removed by precipitation. Nevertheless respiration inhibition tests demonstrated that microorganisms consume more oxygen in the presence of nanoparticles, which suggests a stress situation. It was also observed a slight decrease in the efficiency of nitrification in the presence of nanoparticles. AFM images showed that while the morphology of some organisms remained the same both in the presence and absence of nanoparticles, others assumed a rough surface with hilly like shapes of ca. 50 nm when exposed to nanoparticles. Nanoparticles are thus likely to be either incorporated or adsorbed at the surface of some organisms, increasing the overall respiration rate and decreasing nitrification efficiency. Thus, despite its biocompatibility at macroscopic scale, PBMA is likely to be no longer innocuous at nanoscale.

Risk assessment in occupational exposure to formaldehyde: differences between anatomy and pathology laboratories and formaldehyde-resins production

Formaldehyde (CH2O), the most simple and reactive of all aldehydes, is colorless, and readily polymerizing gas at normal temperature. The most extensive use is in production of resins and has an important application as a disinfectant and preservative, reason why relevant workplace exposure may also occur in pathology and anatomy laboratories and in mortuaries. A study was carried out in Portugal, in a formaldehyde production resins factory and in 10 pathology and anatomy laboratories. It was applied a risk assessment methodology based on Queensland University proposal that permitted to perform risk assessment for each activity developed in a work station. This methodology was applied in 83 different activities developed in the laboratories and in 18 activities of the factory. Also, Micronucleus Test was performed in lymphocytes from 30 factory workers and 50 laboratories workers.

Risk of colorectal cancer associated with the C677T polymorphism in 5,10-methylenetetrahydrofolate reductase in Portuguese patients depends on the intake of methyl-donor nutrients

Background: Polymorphisms located in genes involved in the metabolism of folate and some methyl-related nutrients are implicated in colorectal cancer (CRC). Objective: We evaluated the association of 3 genetic polymorphisms [C677T MTHFR (methylene tetrahydrofolate reductase), A2756G MTR (methionine synthase), and C1420T SHMT (serine hydroxymethyltransferase)] with the intake of methyl-donor nutrients in CRC risk. Design: Patients withCRC(n 196) and healthy controls (n 200) matched for age and sex were evaluated for intake of methyl-donor nutrients and the 3 polymorphisms. Results: Except for folate intake, which was significantly lower in patients (P 0.02), no differences were observed in the dietary intake of other methyl-donor nutrients between groups. High intake of folate ( 406.7 g/d) was associated with a significantly lower risk of CRC (odds ratio: 0.67; 95% CI: 0.45, 0.99). The A2756G MTR polymorphism was not associated with the risk of developing CRC. In contrast, homozygosity for the C677TMTHFRvariant (TT) presented a 3.0-fold increased risk of CRC (95% CI: 1.3, 6.7). Similarly, homozygosity for the C1420T SHMT polymorphism also had a 2.6-fold increased risk (95% CI: 1.1, 5.9) of developing CRC. When interactions between variables were studied, low intake of all methyl-donor nutrients was associated with an increased risk ofCRC in homozygous participants for the C677T MTHFR polymorphism, but a statistically significant interaction was only observed for folate (odds ratio: 14.0; 95% CI: 1.8, 108.5). No significant associations were seen for MTR or SHMT polymorphisms. Conclusion: These results show an association between the C677T MTHFR variant and different folate intakes on risk of CRC.

Genotoxic effects in occupational exposure to formaldehyde: A study in anatomy and pathology laboratories and formaldehyde-resins production

Background - According to the Report on Carcinogens, formaldehyde ranks 25th in the overall U.S. chemical production, with more than 5 million tons produced each year. Given its economic importance and widespread use, many people are exposed to formaldehyde environmentally and/or occupationally. Presently, the International Agency for Research on Cancer classifies formaldehyde as carcinogenic to humans (Group 1), based on sufficient evidence in humans and in experimental animals. Manyfold in vitro studies clearly indicated that formaldehyde can induce genotoxic effects in proliferating cultured mammalian cells. Furthermore, some in vivo studies have found changes in epithelial cells and in peripheral blood lymphocytes related to formaldehyde exposure. Methods - A study was carried out in Portugal, using 80 workers occupationally exposed to formaldehyde vapours: 30 workers from formaldehyde and formaldehyde-based resins production factory and 50 from 10 pathology and anatomy laboratories. A control group of 85 non-exposed subjects was considered. Exposure assessment was performed by applying simultaneously two techniques of air monitoring: NIOSH Method 2541 and Photo Ionization Detection equipment with simultaneously video recording. Evaluation of genotoxic effects was performed by application of micronucleus test in exfoliated epithelial cells from buccal mucosa and peripheral blood lymphocytes. Results - Time-weighted average concentrations not exceeded the reference value (0.75 ppm) in the two occupational settings studied. Ceiling concentrations, on the other hand, were higher than reference value (0.3 ppm) in both. The frequency of micronucleus in peripheral blood lymphocytes and in epithelial cells was significantly higher in both exposed groups than in the control group (p < 0.001). Moreover, the frequency of micronucleus in peripheral blood lymphocytes was significantly higher in the laboratories group than in the factory workers (p < 0.05). A moderate positive correlation was found between duration of occupational exposure to formaldehyde (years of exposure) and micronucleus frequency in peripheral blood lymphocytes (r = 0.401; p < 0.001) and in epithelial cells (r = 0.209; p < 0.01). Conclusions - The population studied is exposed to high peak concentrations of formaldehyde with a long-term exposure. These two aspects, cumulatively, can be the cause of the observed genotoxic endpoint effects. The association of these cytogenetic effects with formaldehyde exposure gives important information to risk assessment process and may also be used to assess health risks for exposed workers.

5' and 3' UTR thymidylate synthase polymorphisms modulate the risk of colorectal cancer independently of the intake of methyl group donors

Thymidylate synthase, as a rate-limiting step in DNA synthesis, catalyses the conversion of dUMP into dTMP using 5,10-methylenotetrahydrofolate as the methyl donor. Two polymorphisms have been described in this gene: a repeat polymorphism in the 5' promoter enhancer region (3R versus 2R) and a 6 bp deletion in the 3' unstranslated region. Both of these may affect protein levels. The present case control study was aimed at investigating the influence of these two polymorphisms on the development of colorectal cancer (CRC), as well as their potential interaction with folate, vitamin B6 and vitamin B12 intake. A total of 196 cases and 200 controls, matched for age and sex distribution, were included in the study. No association was found between CRC and the 28 bp repeat polymorphism, but it was observed that individuals with the 6 bp/del and del/del genotypes had a significantly lower risk of developing the disease (OR=0.47; 95% CI 0.30-0.72). A combined genotype (2R/2R; 6 bp/del+del/del) was also found, which was associated with an even lower risk of developing of the disease (OR=0.42; 95% CI 0.26-0.69). No significant interaction between these polymorphisms and vitamin intake was observed. These results indicate for the first time that the 6 bp/del allele might be a protective factor in the development of CRC, independent of the intake of methyl group donors.

Chiroptical and emissive properties of a calix[4]arene-containing chiral poly (P-phenylene ethynylene) with enantioselective recognition ability

Supramolecular chirality was achieved in solutions and thin films of a calixarene-containing chiral aryleneethynylene copolymer. The observed chiroptical activity, which is primarily allied with the formation of aggregates of high molecular weight polymer chains, is the result of a combination of intrachain and interchain effects. The former arises by the adoption of an induced helix-sense by the polymer main-chain while the latter comes from the exciton coupling of aromatic backbone transitions. The co-existence of bulky bis-calixKlarene units and chiral side-chains on the polymer skeleton prevents efficient pi-stacking of neighbouring chains, keeping the chiral assembly highly emissive. In contrast, for a model polymer lacking calixarene moieties, the chiroptical activity is dominated by strong interchain exciton couplings as a result of more favourable packing of polymer chains, leading to a marked decrease of photoluminescence in the aggregate state. The enantiomeric recognition abilities of both polymers towards (R)- and (S)-alpha-methylbenzylamine were examined. It was found that a significant enantiodiscrimination is exhibited by the calixarene-based polymer in the aggregate state.

Methyl syringate: An efficient phenolic mediator for bacterial and fungal laccases

The aim of the present work is to provide insight into the mechanism of laccase reactions using syringyl-type mediators. We studied the pH dependence and the kinetics of oxidation of syringyl-type phenolics using the low CotA and the high redox potential TvL laccases. Additionally, the efficiency of these compounds as redox mediators for the oxidation of non-phenolic lignin units was tested at different pH values and increasing mediator/non-phenolic ratios. Finally, the intermediates and products of reactions were identified by LC-MS and H-1 NMR. These approaches allow concluding on the (1) mechanism involved in the oxidation of phenolics by bacterial laccases, (2) importance of the chemical nature and properties of phenolic mediators, (3) apparent independence of the enzyme's properties on the yields of non-phenolics conversion, (4) competitive routes involved in the catalytic cycle of the laccase-mediator system with several new C-O coupling type structures being proposed.

Solid-state sensory properties of Calix-Poly(Phenylene Ethynylene)s toward nitroaromatic explosives

This study is primarily focused in establishing the solid-state sensory abilities of several luminescent polymeric calix[4]arene-based materials toward selected nitroaromatic compounds (NACs), creating the foundations for their future application as high performance materials for detection of high explosives. The phenylene ethynylene-type polymers possessing bis-calix[4]arene scaffolds in their core were designed to take advantage of the known recognition abilities of calixarene compounds toward neutral guests, particularly in solid-state, therefore providing enhanced sensitivity and selectivity in the sensing of a given analyte. It was found that all the calix[4]arene-poly(para-phenylene ethynylene)s here reported displayed high sensitivities toward the detection of nitrobenzene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene (TNT). Particularly effective and significant was the response of the films (25-60 nm of thickness) upon exposure to TNT vapor (10 ppb): over 50% of fluorescence quenching was achieved in only 10 s. In contrast, a model polymer lacking the calixarene units showed only reduced quenching activity for the same set of analytes, clearly highlighting the relevance of the macrocyclics in promoting the signaling of the transduction event. The films exhibited high photostability (less than 0.5% loss of fluorescence intensity up to 15 min of continuous irradiation) and the fluorescence quenching sensitivity could be fully recovered after exposure of the quenched films to saturated vapors of hydrazine (the initial fluorescence intensities were usually recovered within 2-5 min of exposure to hydrazine).